Selective blocking of metal surfaces using bifunctional self-assembled monolayers

ABSTRACT

Methods for selectively depositing on metallic surfaces are disclosed. Some embodiments of the disclosure utilize a hydrocarbon having at least two functional groups, at least one functional group selected from amino groups, hydroxyl groups, ether linkages or combinations thereof to form a self-assembled monolayer (SAM) on metallic surfaces.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.63/272,627, filed Oct. 27, 2021, U.S. Provisional Application No.63/304,840, filed Jan. 31, 2022, and U.S. Provisional Application No.63/338,633, filed May 5, 2022, the entire disclosures of which arehereby incorporated by reference herein.

TECHNICAL FIELD

Embodiments of the disclosure generally relate to methods of forming asemiconductor structure. More particularly, some embodiments of thedisclosure are directed to methods of selective deposition onnon-metallic surfaces using self-assembled monolayer using a precursor,wherein the precursor comprises at least two functional groups selectedfrom alkene, alkyne, ketone, hydroxyl, aldehyde, ester, or combinationsthereof.

BACKGROUND

Generally, an integrated circuit (IC) refers to a set of electronicdevices, e.g., transistors formed on a small chip of semiconductormaterial, typically, silicon. Typically, the IC includes one or morelayers of metallization having metal lines to connect the electronicdevices of the IC to one another and to external connections. Typically,layers of the interlayer dielectric material are placed between themetallization layers of the IC for insulation.

As the size of the IC decreases, the spacing between the metal linesdecreases. Typically, to manufacture an interconnect structure, a planarprocess is used that involves aligning and connecting one layer ofmetallization to another layer of metallization.

Reducing the resistance of the via is critical for improved performanceof the electronic device. The via resistance reduction is usuallycontrolled by minimizing cladding and by reducing the resistivity of thevia material.

Therefore, there is an ongoing need in the art for a methods of reducingvia resistance.

SUMMARY

One or more embodiments of the disclosure are directed to a method offorming a semiconductor structure. In some embodiments, the methodcomprises selectively depositing a self-assembled monolayer (SAM) on afirst surface of a substrate by exposing the substrate to a firstprecursor, wherein the substrate has at least one feature comprising thefirst surface and a second surface and wherein the first precursorcomprises at least two functional groups, at least one functional groupselected from amino groups, hydroxyl groups, ether linkages orcombinations thereof, selectively depositing a liner on the secondsurface by exposing the substrate to a second precursor, and removingthe self-assembled monolayer. In some embodiments, the first surfacecomprises a metal. In some embodiments, the second surface comprises adielectric material.

In one or more embodiments, the method comprises exposing a substrate toat least one first precursor to selectively deposit a self-assembledmonolayer (SAM) on a first surface of the substrate, the substratehaving at least one feature comprising the first surface and a secondsurface, exposing the substrate to a second precursor to selectivelydeposit a liner on the second surface, and removing the self-assembledmonolayer (SAM). In some embodiments, the first surface comprises ametal selected from one or more of copper (Cu), cobalt (Co), ruthenium(Ru), tungsten (W) and molybdenum (Mo). In some embodiments, the secondsurface comprises a dielectric material. In some embodiments, the firstprecursor has a molecular weight in a range of from 50 Daltons to 500Daltons. In some embodiments, the first precursor has a vapor pressurein a range of from 100 mTorr to 100 Torr at 120° C. In some embodiments,the first precursor is selected from the group consisting of structuresof Formula (xiv) or Formula (xvi)

wherein each n is independently 1-20 and each R is independentlyselected from H, C1-C10 alkyl or aryl groups.

In one or more embodiments, the method comprises exposing a substrate toat least one first precursor to selectively deposit a self-assembledmonolayer (SAM) on a first surface of the substrate, the substratehaving at least one feature comprising the first surface and a secondsurface, exposing the substrate to a second precursor to selectivelydeposit a liner on the second surface, and removing the self-assembledmonolayer (SAM). In some embodiments, the first surface comprises ametal selected from one or more of copper (Cu), cobalt (Co), ruthenium(Ru), tungsten (W) and molybdenum (Mo). In some embodiments, the secondsurface comprises a dielectric material. In some embodiments, the firstprecursor has a molecular weight in a range of from 50 Daltons to 500Daltons. In some embodiments, the first precursor has a vapor pressurein a range of from 100 mTorr to 100 Torr at 120° C. In some embodiments,the first precursor is selected from the group consisting of structuresof Formula (xix) through Formula (xxvii)

wherein each R is independently selected from H, C1-C10 alkyl or arylgroups.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments.

FIG. 1 illustrates a process flow diagram of a method according to oneor more embodiments of the disclosure;

FIGS. 2A-2F illustrate cross-sectional views of an exemplary substrateduring processing according to one or more embodiments of thedisclosure; and

FIG. 3 illustrates an exemplary cluster tool according to one or moreembodiments of the disclosure.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the disclosure, it isto be understood that the disclosure is not limited to the details ofconstruction or process steps set forth in the following description.The disclosure is capable of other embodiments and of being practiced orbeing carried out in various ways.

As used in this specification and the appended claims, the term“substrate” refers to a surface, or portion of a surface, upon which aprocess acts. It will also be understood by those skilled in the artthat reference to a substrate can also refer to only a portion of thesubstrate unless the context clearly indicates otherwise. Additionally,reference to depositing on a substrate can mean both a bare substrateand a substrate with one or more films or features deposited or formedthereon

A “substrate” as used herein, refers to any substrate or materialsurface formed on a substrate upon which film processing is performedduring a fabrication process. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, amorphous silicon, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure and/orbake the substrate surface. In addition to film processing directly onthe surface of the substrate itself, in the present disclosure, any ofthe film processing steps disclosed may also be performed on anunderlayer formed on the substrate as disclosed in more detail below,and the term “substrate surface” is intended to include such underlayeras the context indicates. Thus, for example, where a film/layer orpartial film/layer has been deposited onto a substrate surface, theexposed surface of the newly deposited film/layer becomes the substratesurface.

“Atomic layer deposition” or “cyclical deposition” as used herein refersto the sequential exposure of two or more reactive compounds to deposita layer of material on a substrate surface. As used in thisspecification and the appended claims, the terms “reactive compound”,“reactive gas”, “reactive species”, “precursor”, “process gas” and thelike are used interchangeably to mean a substance with a species capableof reacting with the substrate surface or material on the substratesurface in a surface reaction (e.g., chemisorption, oxidation,reduction). The substrate, or portion of the substrate, is exposed tothe precursors (or reactive gases) sequentially or substantiallysequentially. As used herein throughout the specification,“substantially sequentially” means that a majority of the duration of aprecursor exposure does not overlap with the exposure to a co-reagent,although there may be some overlap.

A metal can be grown by atomic layer deposition for many applications.One or more embodiments of the disclosure advantageously provideprocesses for atomic layer deposition to form metal-containing films. Asused in this specification and the appended claims, the term“metal-containing film” refers to a film that comprises metal atoms andhas greater than or equal to about 1 atomic % metal, 2 atomic % metal, 3atomic % metal, 4 atomic % metal, 5 atomic % metal, 10 atomic % metal,15 atomic % metal, 20% atomic metal, 25% atomic metal, 30% atomic metal,35% atomic metal, 40% atomic metal, 45% atomic metal, 50% atomic metal,55% atomic metal, 60% atomic metal, or 65% atomic metal. In someembodiments, the metal-containing film comprises one or more of a metal,a metal nitride, a metal carbide, or a metal oxide. The skilled artisanwill recognize that the use of molecular formula like MO, where M is ametal, does not imply a specific stoichiometric relationship between theelements but merely the identity of the major components of the film.For example, MO refers to a film whose major composition comprises ametal and oxygen atoms. In some embodiments, the major composition ofthe specified film (i.e., the sum of the atomic percent of the specifiedatoms) is greater than or equal to about 95%, 98%, 99% or 99.5% of thefilm, on an atomic basis.

The phrase “metallic material surface” or “non-metallic materialsurface” as used herein refers to the surface of a metallic ornon-metallic material, respectively. A non-metallic material, for thepurposes of this disclosure, is any material that exhibits theproperties of a poor conductor, or a good insulator. A non-metallicmaterial may include metal atoms (e.g., tantalum nitride, titaniumnitride) and still fall into the scope of non-metallic materials. Insome embodiments, the term “conductive material” is used in place ofmetallic material. In some embodiments, the term “dielectric material”is used in place of non-metallic material.

The phrase “selectively depositing on a first surface over a secondsurface”, and the like, as used herein means that a first amount orthickness is deposited on the first surface and a second amount orthickness is deposited on the second surface, where the second amount orthickness is less than the first amount or thickness, or, in someembodiments, no amount is deposited on the second surface.

The term “over” as used herein does not imply a physical orientation ofone surface on top of another surface, rather a relationship of thethermodynamic or kinetic properties of the chemical reaction with onesurface relative to the other surface. For example, selectivelydepositing a film onto a metallic material surface over a non-metallicmaterial surface means that the film deposits on the metallic materialsurface and less or no film deposits on the non-metallic materialsurface; or that the formation of the film on the metallic materialsurface is thermodynamically or kinetically favorable relative to theformation of a film on the non-metallic material surface.

Reducing contact resistance (Rc) for 3 nm node (N3) and beyondsemiconductor structures is critical. One or more embodiments of thisdisclosure are directed to methods of selectively forming aself-assembled monolayer (SAM) on a first surface of a substrate over asecond surface. The substrate comprises a metallic material (conductivematerial) with a first surface and a non-metallic material (dielectricmaterial) with a second surface. In some embodiments, the first surfacemay be described as a metallic material surface or conductive materialsurface. In some embodiments, the first surface comprises one or more ofcopper (Cu), cobalt (Co), ruthenium (Ru), tungsten (W), and molybdenum(Mo). In some embodiments, the second surface may be described as anon-metallic material surface or a dielectric material surface. In someembodiments, the method described herein have middle end of line (MEOL)and back end of line (BEOL) applications.

With reference to FIG. 1 , which is a process flow diagram, one or moreembodiments of the disclosure are directed to a method 100 of forming anelectronic device. The method illustrated in FIG. 1 is representative ofan integrated process.

FIGS. 2A thru 2F illustrate cross-sectional views of an exemplary device200 during the processing method 100 according to one or moreembodiments of the disclosure. Referring to FIG. 2A, a substrate 210 isprovided having a barrier layer 215, a metal liner 220, a conductivelayer 225, an etch stop layer 230, and a dielectric layer 235 thereon.In one or more embodiments, the dielectric layer 235 has at least onefeature 240. In some embodiments, the substrate 210 is a wafer, forexample a semiconductor substrate. In some embodiments, the substrate210 is an etch stop layer on a wafer.

For illustrative purposes, FIG. 2A shows the substrate 210 having asingle feature 240. One skilled in the art, however, will understandthat there can be more than one feature. As shown in FIG. 2A, thefeature 240 includes a first surface 245 and a second surface 250. Insome embodiments, the first surface 245 is a bottom surface of thefeature 240. In some embodiments, the second surface 250 is a sidewallof the feature 240. The shape of the feature 240 can be any suitableshape including, but not limited to, trenches, vias that, when filledwith metal, transfer current between layers, and lines that transfercurrent within the same device layer. It will be appreciated that in oneor more embodiments, the conductive layer 225 forms a metal line thattransfers current within the same device layer. In some embodiments, thefeature 240 defines a gap in the dielectric layer 235. As used herein,the term “feature” refers to any intentional surface irregularity.Suitable examples of features include, but are not limited to, trencheswhich have a top, two sidewalls, and a bottom, peaks which have a topand two sidewalls. Features can have any suitable aspect ratio (ratio ofthe depth of the feature to the width of the feature). In someembodiments, the aspect ratio is greater than or equal to about 1:1,2:1, 3:1, 4:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1 or 40:1.

In one or more embodiments, the barrier layer 215 is a conformal layer.The barrier layer 215 may comprise any suitable material known to theskilled artisan and may be deposited by any suitable technique known tothe skilled artisan. In some embodiments, the barrier layer is selectedfrom titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride(WN). In specific embodiments, the barrier layer 215 comprises tantalumnitride (TaN). In some embodiments, the barrier layer 215 is formed byALD. In some embodiments, the barrier layer 215 prevents diffusion ofmaterial across itself to layers below.

In one or more embodiments, the metal liner 220 may comprise anysuitable metal material known to the skilled artisan and may bedeposited by any technique known to the skilled artisan. In one or moreembodiments, the metal liner 220 comprises one or more of copper (Cu),cobalt (Co), ruthenium (Ru), iridium (Ir), rhodium (Rh), molybdenum(Mo), tungsten (W), aluminum (Al), nickel (Ni), and platinum (Pt). Inone or more embodiments, the metal liner 220 comprises one or more of asingle layer of tungsten (W) or a single layer of molybdenum (Mo). Insome embodiments, the metal liner 220 comprises or consists essentiallyof tungsten or molybdenum. As used in this specification and theappended claims, the term “consists essentially of” means that thematerial is greater than or equal to about 95%, 98% or 99% of the statedmaterial on an atomic basis.

In one or more embodiments, the conductive layer 225 comprises a metalor a metallic material. In some embodiments, the metal or metallicmaterial can be any suitable metallic material. In some embodiments, themetallic materials of this disclosure are conductive materials. Suitablemetallic materials include, but are not limited to, metals, conductivemetal nitrides, conductive metal oxides, metal alloys, silicon,combinations thereof, and other conductive materials.

As used in this specification and the appended claims, the term “oxide”or the like means that the material contains the specified element(s).The term should not be interpreted to imply a specific ratio ofelements. Accordingly, an “oxide” or the like may comprise astoichiometric ratio of elements or a non-stoichiometric ratio ofelements.

In one or more embodiments, the metal or metallic material may compriseany suitable metal known to the skilled artisan. In some embodiments,the metal or metallic material is selected from one or more of copper(Cu), cobalt (Co), ruthenium (Ru), iridium (Ir), rhodium (Rh),molybdenum (Mo), tungsten (W), aluminum (Al), nickel (Ni), and platinum(Pt). In some embodiments, the metal or metallic material consistsessentially of copper (Cu), cobalt (Co), ruthenium (Ru), iridium (Ir),rhodium (Rh), molybdenum (Mo), tungsten (W), aluminum (Al), nickel (Ni),or platinum (Pt). In some embodiments, the metal or metallic materialconsists essentially of copper, cobalt, ruthenium, tungsten, ormolybdenum. In some embodiments, the metallic material comprises orconsists essentially of tungsten or molybdenum.

In one or more embodiments, the etch stop layer 230 comprises anysuitable material known to the skilled artisan. In one or moreembodiments, the etch stop layer 230 comprises one or more of siliconnitride (SiN), silicon carbide (SiC), aluminum oxide (AlO_(x)), andaluminum nitride (AlN). In some embodiments, the etch stop layer 230 maybe deposited using a technique selected from CVD, PVD, and ALD.

In one or more embodiments, a portion of the metal liner 220 and theetch stop layer 230 are removed and the bottom first surface 245 of theat least one feature 240 is exposed. In some embodiments, the bottomfirst surface 245 is a portion of the top surface of the conductivematerial 225, such that a portion of the conductive material 225 isexposed.

In one or more embodiments, the dielectric layer 235 can be any suitablematerial. In some embodiments, the dielectric layer 235 insulatesadjacent devices and prevent leakage. Suitable dielectric materialsinclude, but are not limited to, silicon oxides (e.g., SiO₂), siliconnitrides (e.g., SiN), silicon carbides (e.g., SiC), and combinationsthereof (e.g., SiCON). Suitable dielectric materials further includealuminum oxide, aluminum nitride, and low-k dielectric materials. Insome embodiments, the dielectric material consists essentially ofsilicon dioxide (SiO₂). In some embodiments, the dielectric layer 235comprises silicon nitride. In some embodiments, the dielectric layer 235consists essentially of silicon nitride.

In one or more embodiments, the dielectric layer 235 is deposited usingany suitable deposition technique, such as, but not limited to, chemicalvapor deposition (“CVD”), physical vapor deposition (“PVD”), molecularbeam epitaxy (“MBE”), metalorganic chemical vapor deposition (“MOCVD”),atomic layer deposition (“ALD”), spin-on, or other deposition techniquesknown to one of ordinary skill in the art of microelectronic devicemanufacturing.

In one or more embodiments, the substrate 210 is independentlymaintained at an operating pressure during one or more operations of themethod 100. In some embodiments, the operating pressure is less than orequal to 100 Torr, less than or equal to 80 Torr, less than or equal to70 Torr, less than or equal to 60 Torr, less than or equal to 50 Torr,less than or equal to 40 Torr, less than or equal to 30 Torr, less thanor equal to 20 Torr, less than or equal to 15 Torr, less than or equalto 10 Torr, less than or equal to 5 Torr, less than or equal to 1 Torr,less than or equal to 500 mTorr, less than or equal to 200 mTorr, lessthan or equal to 100 mTorr, or less than or equal to 50 mTorr. In someembodiments, the operating pressure is 10 Torr, 20 Torr, 30 Torr, 40Torr, 50 Torr or 100 Torr. In some embodiments, the substrate 210 ismaintained at a pressure in a range of from 1 mTorr to 100 Torr, from 1mTorr to 80 Torr, from 1 mTorr to 60 Torr, from 1 mTorr to 40 Torr, from1 mTorr to 20 Torr, from 1 mTorr to 10 Torr, from 1 mTorr to 5 Torr,from 1 mTorr to 1 Torr, from 1 mTorr to 500 mTorr, from 1 mTorr to 200mTorr, from 1 mTorr to 100 mTorr, from 1 mTorr to 50 Torr, from 500mTorr to 100 Torr, from 500 mTorr to 80 Torr, from 500 mTorr to 60 Torr,from 500 mTorr to 40 Torr, from 500 mTorr to 20 Torr, from 500 mTorr to10 Torr, from 500 mTorr to 5 Torr, from 500 mTorr to 1 Torr, from 1 Torrto 100 Torr, from 1 Torr to 80 Torr, from 1 Torr to 60 Torr, from 1 Torrto 40 Torr, from 1 Torr to 20 Torr, from 1 Torr to 10 Torr, from 1 Torrto 5 Torr, from 10 Torr to 100 Torr, from 10 Torr to 80 Torr, from 10Torr to 60 Torr, from 10 Torr to 40 Torr, from 10 Torr to 20 Torr, from20 Torr to 100 Torr, from 20 Torr to 80 Torr, from 20 Torr to 60 Torr,or from 20 Torr to 40 Torr during depositing the self-assembledmonolayer (SAM) 255.

In some embodiments, the temperature of the substrate is controlledduring the method 100. The temperature of the substrate may also bereferred to as the operating temperature. In some embodiments, theoperating temperature is less than or equal to 450° C., less than orequal to 400° C., less than or equal to 350° C., less than or equal to300° C., less than or equal to 275° C., less than or equal to 250° C.,less than or equal to 225° C., less than or equal to 200° C., less thanor equal to 150° C., less than or equal to 100° C., or less than orequal to 80° C. In some embodiments, the operating temperature in arange of from 60° C. to 450° C., from 60° C. to 350° C., from 60° C. to250° C., from 60° C. to 150° C., from 60° C. to 100° C., from 100° C. to450° C., from 100° C. to 350° C., from 100° C. to 250° C., from 100° C.to 200° C., from 200° C. to 450° C., from 200° C. to 350° C., from 200°C. to 300° C., from 300° C. to 450° C., from 300° C. to 350° C., or from400° C. to 450° C. during depositing the self-assembled monolayer (SAM)255.

Referring to FIG. 1 , an exemplary method 100 begins with an optionalpre-cleaning operation 102. The pre-cleaning operation can be anysuitable pre-cleaning process known to the skill artisan. Suitablepre-cleaning operations include, but are not limited to, soaking, nativeoxide remove, and the like. In some embodiments the pre-cleaningoperation 102 cleans the first surface 245 and the second surface 250.In some embodiments the pre-cleaning operation 102 results in theformation of a surface of the substrate 210, e.g., the first surface 245and/or the second surface 250, substantially free of oxide. As usedherein, the term “substantially free of oxide” means that the surfacehas less than 10%, less than 5%, less than 4%, less than 3%, less than2%, or less than 1% oxygen on atomic basis.

At operation 104, the substrate 210 is exposed to a first precursor todeposit a self-assembled monolayer (SAM) 255. As used herein, the phrase“the substrate is exposed to” means that the substrate, as a whole,including the individual materials and layers thereon are exposed to thestated process or condition. FIG. 2B illustrates the self-assembledmonolayer (SAM) 255 deposited on the first surface 245 of the feature240. In some embodiments, the self-assembled monolayer (SAM) 255 isselectively deposited on the first surface 245 of the feature 240 overthe second surface 250. In some embodiments, the self-assembledmonolayer (SAM) is not deposited on the second surface 250 of thefeature 240. In one or more embodiments, the self-assembled monolayer(SAM) 255 is deposited on the exposed first surface 245 of theconductive layer 225 in the bottom of the feature 240. It is noted that,as described above, a portion of the metal liner 220 and a portion ofthe etch stop layer 230 are removed, e.g., by etching, to expose aportion, e.g., the first surface 245 of the conductive layer 225 in thebottom of the feature 240. In some embodiments, operation 104 is a drydeposition process.

In some embodiments, “selectively” means that the subject material formson the selected surface at a rate greater than or equal to about 1.5×,2×, 3×, 4×, 5×, 7×, 10×, 15×, 20×, 25×, 30×, 35×, 40×, 45×, or 50×therate of formation on the non-selected surface. Stated differently, theselectivity of the stated process for the selected surface relative tothe non-selected surface is greater than or equal to about 3:2, 2:1,3:1, 4:1, 5:1, 7:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, or50:1.

In one or more embodiments, the first precursor reversibly binds to themetal. In some embodiments, the self-assembled monolayer (SAM) 255formed by the first precursor remains substantially intact during thesubsequent operations of the method 100. As used herein, the term“substantially” refers to up to 99%, 98%, 95%, 90%, or 80% of theself-assembled monolayer (SAM) 255 remains intact during the subsequentoperations of the method 100.

In some embodiments, the first precursor comprises at least one, atleast two, or at least three functional groups. In some embodiments, thefunctional groups are designed to allow reverse selective ALDdeposition. In some embodiments, the functional group comprisesunsaturated hydrocarbon (e.g., alkene, alkyne, phenyl or combinationsthereof), ketone, hydroxyl, aldehyde, ester, or combinations thereof. Insome embodiments, the first precursor comprises at least one unsaturatedgroup. In some embodiments, the first precursor comprises at least onehydroxyl group. In some embodiments, the first precursor comprises atleast one aldehyde group. In some embodiments, the first precursorcomprises at least one ketone group. In some embodiments, the firstprecursor comprises at least one ester group. In some embodiments, thefirst precursor comprises at least two functional groups. In someembodiments, the at least two functional groups are independentlyselected from an unsaturated hydrocarbon (e.g., alkene, alkyne, phenylor combinations thereof), a ketone, a hydroxyl, an aldehyde, an ester,or a derivative thereof. In some embodiments, each of the at least threefunctional groups are independently selected from an unsaturatedhydrocarbon (e.g., alkene, alkyne, phenyl or combination thereof), aketone, a hydroxyl, an aldehyde, an ester, or a derivative thereof. Insome embodiments, surface engineering with bifunctional groups allowsreverse selective ALD deposition to electrical resistance at a viacontact interface. In some embodiments, the bifunctional group functionsas a conjugate system. In some embodiments, the conjugate systemcomprises a lone electron pair group.

Without intending to be bound by theory, it is believed that thed-orbitals of the metallic materials start to share electrons with thesp² orbitals of the unsaturated hydrocarbon. Accordingly, in someembodiments, the unsaturated hydrocarbon comprises at least one compoundwith at least one double bond between two carbon atoms. In someembodiments, the unsaturated hydrocarbon comprises at least one compoundwith at least one triple bond between two carbon atoms. Stateddifferently, in some embodiments, the unsaturated hydrocarbon comprisesat least one compound with a general formula according to formula (i) orformula (ii):

In some embodiments, the R₁, R₂, R₃, R₄, R₅ and R₆ are independentlyselected from H, —R₇OH, —CH(OH)R₈, —C(OH)R₉R₁₀, and —COR₁₁. In someembodiments, the R₇, R₈, R₉, R₁₀ and R₁₁ are independently selected fromH and alkyl group. As used in this regard, the alkyl group contains 1-30carbon atoms. In some embodiments, the alkyl group contains 1-4 carbonatoms. In some embodiments, the alkyl group is a linear group (e.g., astraight-chain saturated or unsaturated hydrocarbon). In someembodiments, the alkyl group is a branched group (e.g., a branchedsaturated or unsaturated hydrocarbon). In some embodiments, the alkylgroup is a cyclic group (e.g., a cyclic saturated or unsaturatedhydrocarbon).

Without intending to be bound by theory, it is believed that thelikelihood of polymerization advantageously increases as the number ofmultiple unsaturated bonds increases. The polymerization may make theself-assembled monolayer (SAM) 255 falling off harder during thesubsequent operations of the method 100. Further, without intending tobe bound by theory, it is believed that the unsaturated hydrocarbon, theself-assembled monolayer (SAM) 255, suppresses one or more of thenucleation or growth rate of a subsequent film on the first surface 245.Accordingly, in some embodiments, the first precursor comprises at leastone unsaturated bond, wherein the first surface 245 comprises copper,cobalt, ruthenium, tungsten, molybdenum, or combinations thereof.

In some embodiments, a precursor with a single hydroxyl group iseffective to allow reverse selective ALD deposition. In someembodiments, the self-assembled monolayer (SAM) 255 formed with aprecursor comprising a single hydroxyl group impacts the etch stop layer230 and/or modifies the non-metallic surface 250. Accordingly, in one ormore embodiments, the bifunctional groups with lone electron pairs andconjugated system are designed for the metallic surface 245 comprisingcopper, cobalt, ruthenium, tungsten, molybdenum, or combinationsthereof. In other words, in some embodiments, the self-assembledmonolayer (SAM) 255 selectively blocks metallic surface 245 and yetkeeps the non-metallic surface 250 intact during subsequent operationsof the method 100, wherein the metallic surface 245 comprises copper,cobalt, ruthenium, tungsten, molybdenum, or combinations thereof.

In some embodiments, the first precursor comprises a structure accordingto Formula (iii), wherein R₇ is selected from H and C₁-C₄ group, andwherein R₈ is C₁-C₄ group.

In some embodiments, the first precursor comprises a structure accordingto Formula (iv), wherein each of R₇ and R₉ are independently selectedfrom H and C₁-C₄ group.

In some embodiments, the first precursor comprises a structure accordingto Formula (v), wherein each of R₇ and R₁₀ are independently selectedfrom H and C₁-C₄ group.

In some embodiments, the first precursor comprises a structure accordingto Formula (v), wherein each of R₁₁, R₁₂, R₁₃ and R₁₄ are independentlyselected from H and C₁-C₄ group.

In some embodiments, the first precursor is selected from the groupconsisting of structures of Formula (vi), Formula (vii), Formula (viii),Formula (ix), Formula (x), Formula (xi), Formula (xii) and Formula(xiii).

In some embodiments, a precursor with two functional groups allowsreverse selective ALD deposition. In some embodiments, theself-assembled monolayer (SAM) 255 formed with a precursor comprising atleast two function groups where at least one functional group isselected from amino groups, hydroxyl groups, ether linkages orcombinations thereof to impact the etch stop layer 230 and/or modifiesthe non-metallic surface 250. Accordingly, in some embodiments, theself-assembled monolayer (SAM) 255 selectively blocks metallic surface245 and yet keeps the non-metallic surface 250 intact during subsequentoperations of the method 100, wherein the metallic surface 245 comprisescopper, cobalt, ruthenium, tungsten, molybdenum, or combinationsthereof.

In some embodiments, the first precursor comprises a structure of any ofFormula (xiv) or Formula (xvi)

where each n is independently 1-20 and each R is independently selectedfrom H, C1-C10 alkyl or aryl groups.

In some embodiments, the first precursor comprises a structure of any ofFormula (xix) through Formula (xxvii)

where each R is independently selected from H, C1-C10 alkyl or arylgroups.

In one or more embodiments, the first precursor has a molecular weightin a range of from 50 Dalton to 500 Dalton, from 100 Dalton to 500Dalton, from 200 Dalton to 500 Dalton, from 300 Dalton to 500 Dalton,from 400 Dalton to 500 Dalton, from 50 Dalton to 400 Dalton, from 100Dalton to 400 Dalton, from 200 Dalton to 400 Dalton, from 300 Dalton to400 Dalton, from 50 Dalton to 300 Dalton, from 100 Dalton to 300 Dalton,from 200 Dalton to 300 Dalton, from 50 Dalton to 200 Dalton, from 100Dalton to 200 Dalton or from 50 Dalton to 100 Dalton. In someembodiments, the first precursor has a molecular weight less than 500Dalton, less than 400 Dalton, less than 300 Dalton or less than 100Dalton.

In one or more embodiments, the first precursor has a vapor pressure ina range of from 100 mTorr to 100 Torr, from 300 mTorr to 100 Torr, from500 mTorr to 100 Torr, from 800 mTorr to 100 Torr, from 100 mTorr to 50Torr, from 300 mTorr to 50 Torr, from 500 mTorr to 50 Torr, from 800mTorr to 50 Torr, from 100 mTorr to 10 Torr, from 300 mTorr to 10 Torr,from 500 mTorr to 10 Torr, from 800 mTorr to 10 Torr, from 100 mTorr to1 Torr, from 300 mTorr to 1 Torr, from 500 mTorr to 1 Torr, from 800mTorr to 1 Torr, from 100 mTorr to 8 mTorr, from 300 mTorr to 800 mTorr,from 500 mTorr to 800 mTorr, from 100 mTorr to 500 mTorr, from 300 mTorrto 500 mTorr or from 100 mTorr to 300 mTorr at 120° C. in someembodiments, the first precursor has a vapor pressure more than 100mTorr, more than 300 mTorr, more than 500 mTorr, more than 800 mTorr,more than 1 Torr, more than 10 Torr, more than 50 Torr or more than 90Torr.

In one or more embodiments, the substrate 210 can be exposed to thefirst precursor at any suitable flow rate to form the self-assembledmonolayer (SAM) 255. In some embodiments, the substrate 210 is exposedto the first precursor at a flow rate in a range of from 50 sccm to 2000sccm, from 100 sccm to 2000 sccm, from 500 sccm to 2000 sccm, from 1000sccm to 2000 sccm, from 1500 sccm to 2000 sccm, from 50 sccm to 100sccm, from 75 sccm to 100 sccm. In some embodiments, the flow rate ofthe first precursor is less than or equal to 2000 sccm, less than orequal to 1500 sccm, less than or equal to 1000 sccm, less than or equalto 600 sccm, less than or equal to 500 sccm, less than or equal to 400sccm, less than or equal to 300 sccm, less than or equal to 250 sccm,less than or equal to 200 sccm, less than or equal to 150 sccm, lessthan or equal to 100 sccm, less than or equal to 75 sccm, or less thanor equal to 50 sccm.

In some embodiments, the substrate 210 is soaked in a vapor of the firstprecursor. In some embodiments, the soak period can be any suitableperiod for forming the self-assembled monolayer (SAM) 255. In someembodiments, the soak period is greater than or equal to 10 s, greaterthan or equal to 20 s, greater than or equal to 30 s, greater than orequal to 45 s, greater than or equal to 60 s, greater than or equal to80 s, greater than or equal to 120 s, greater than or equal to 150 s, orgreater than or equal to 200 s.

In one or more embodiments, the first precursor is liquid at theoperating temperature and/or operating pressure. In one or moreembodiments, the first precursor is solid at the operating temperatureand/or operating pressure. In some embodiments, the first precursor isstored in an ampoule or a cylinder, from which the first precursor isdelivered to the substrate 210. In some embodiments, the first precursorhas a vapor pressure in a range of from 0.1 Torr to 150 Torr, from 0.1Torr to 100 Torr, from 0.1 Torr to 50 Torr, from 0.1 Torr to 10 Torr,from 0.1 Torr to 1 Torr, from 0.1 Torr to 0.5 Torr, from 0.5 Torr to 150Torr, from 0.5 Torr to 100 Torr, from 0.5 Torr to 50 Torr, from 0.5 Torrto 10 Torr, from 0.5 Torr to 1 Torr, from 1 Torr to 150 Torr, from 1Torr to 100 Torr, from 1 Torr to 50 Torr, from 1 Torr to 10 Torr, from10 Torr to 150 Torr, from 10 Torr to 100 Torr, from 10 Torr to 50 Torr,from 50 Torr to 150 Torr, from 50 Torr to 100 Torr, or from 100 Torr to150 Torr at the operating temperature and/or operating pressure. In someembodiments, the first precursor has a vapor pressure greater than orequal to about 0.1 Torr at the operating temperature and/or operatingpressure.

In one or more embodiments, the first precursor is substantially freefrom one or more of metal, halogen or nitrogen. As used in this manner,the term “substantially free” means that the first precursor has lessthan 10% weight on atomic basis, less than 5% weight on atomic basis,less than 3% weight on atomic basis or less than 1% weight on atomicbasis.

In one or more embodiments, the first precursor further comprises acarrier gas. In some embodiments, the carrier gas is a non-reactive gas.In some embodiments, the carrier gas comprises a noble gas. In someembodiments, the noble gas includes one or more of helium (He), neon(Ne), or argon (Ar). In some embodiments, the carrier gas comprisesargon (Ar).

In some embodiments, a flow of the carrier gas is configured to carrythe first precursor from a container to the substrate 210. In someembodiments, the flow rate of the argon (Ar) gas that is configured tocarry the first precursor to the substrate 210 is controlled.

Referring to FIG. 1 , at operation 106, the substrate 210 is exposed toa second precursor for selectively depositing a liner on the secondsurface 250. FIG. 2C illustrates the liner 260 being selectivelydeposited on the second surface 250. In some embodiments, the liner 260is formed on the second surface 250 and not on the first surface 245. Insome embodiments, the liner 260 is a conformal layer. The liner 260 maycomprise any suitable material known to the skilled artisan and may bedeposited by any suitable technique known to the skilled artisan. Insome embodiments, the liner 260 comprises a metal nitride. In someembodiments, the liner 260 comprises tantalum nitride (TaN), titaniumnitride (TiN), or combinations thereof. In some embodiments, the liner260 has the same properties as the barrier layer 215. In someembodiments, the liner 260 is selectively deposited by atomic layerdeposition (ALD). In some embodiments, the self-assembled monolayer(SAM) 255 selectively blocks metal interface 245 and yet keeps thenon-metallic surface 250 intact for selective ALD deposition. In someembodiments, the liner 260 is deposited by sequentially exposing thesubstrate 210 to a metal precursor and a reactant. In some embodiments,the liner 260 is formed without the use of plasma. In some embodiments,the liner 260 has a thickness in a range of from about 2 Å to about 20Å. In some embodiments, the liner 260 is formed in a single ALD cycle.In some embodiments, the liner 260 is formed in from 1 to 40 ALD cycles.In one or more embodiments, each cycle of the 1 to 40 ALD cycles isconfigured to deposit a thickness of about 0.5 Å of the liner 260.

Referring to FIG. 1 , at operation 108, the self-assembled monolayer(SAM) 255 is removed. FIG. 2D illustrates the self-assembled monolayer(SAM) 255 removed from the first surface 245. The self-assembledmonolayer (SAM) 255 is removed by an etch process. In some embodiments,the etch process may comprise any suitable means, including but notlimited to, plasma cleaning processes. In one or more embodiments, theself-assembled monolayer (SAM) 255 is removed by a plasma treatment. Insome embodiments, the plasma comprises one or more of hydrogen (H₂),nitrogen (N₂), or argon (Ar) plasma. As used in this specification, aplasma comprising hydrogen, nitrogen, or argon, means a plasma formedfrom the molecular form of the species named. In some embodiments, theplasma consists essentially of hydrogen, nitrogen, argon, orcombinations thereof. In some embodiments, the self-assembled monolayer(SAM) 255 is removed without causing substantially damage to the liner260.

The power of the plasma may be varied depending on the composition,packing and/or thickness of the self-assembled monolayer (SAM) andcomposition and/or thickness of the surrounding materials. In someembodiments, the plasma power is in a range of about 20 W to about 500W, in a range of about 20 W to about 400 W, in a range of about 20 W toabout 250 W, in a range of about 50 W to about 500 W, in a range ofabout 100 W to about 500 W, in a range of about 100 W to about 450 W, ina range of about 100 W to about 500 W, or in a range of about 200 W toabout 400 W. In some embodiments, the plasma power is about 50 W, about200 W or about 400 W.

The duration of the plasma exposure may be varied depending on thecomposition, packing and/or thickness of the self-assembled monolayer(SAM) 255 and composition and/or thickness of the surrounding materials.In some embodiments, the substrate is exposed to the plasma for a timeperiod in a range of about 2 s to about 60 s, in a range of about 3 s toabout 30 s, or in a range of about 5 s to about 10 s. In someembodiments, the substrate is exposed to the plasma for a time period ofabout 3 s, about 5 s, about 10 s, or about 30 s.

Referring to FIG. 1 and to FIG. 2E, at operation 110, an adhesion layer265 is deposited on the barrier layer 260 and the first surface 245.FIG. 2F illustrates the adhesion layer 265 deposited on the barrierlayer 260 and the first surface 245. In some embodiments, the adhesionlayer 265 is conformally deposited on the barrier layer 260 and thefirst surface 245. In some embodiments, the thickness of the adhesionlayer 265 on the barrier layer 260 is same as the thickness of theadhesion layer 265 on the first surface 245. In some embodiments, thethickness of the adhesion layer 265 on the barrier layer 260 isdifferent from the thickness of the adhesion layer 265 on the firstsurface 245. In some embodiments, the thickness of the adhesion layer265 on the barrier layer 260 that is greater than the thickness of theadhesion layer 265 on the first surface 245. In some embodiments, theadhesion layer 265 comprises any suitable material known to the skilledartisan and may be deposited by any suitable technique known to theskilled artisan.

Referring to FIG. 1 and FIG. 2F, at operation 112, the method 100includes depositing a conductive material 270 in the at least onefeature 240 by exposing the substrate to a third precursor. In someembodiments, the third precursor comprises a metal. In some embodiments,the third precursor comprises copper, cobalt, ruthenium, tungsten,molybdenum, or combinations thereof. In some embodiments, the conductivematerial 270 is deposited by a gap fill process on the adhesion layer265. In some embodiments, the gap fill process comprises a bottom-upfill or a conformal fill. FIG. 2G shows the conductive material 270forming the interconnect within the feature 245.

The conductive material 270 can be any suitable material known to theskilled artisan. In some embodiments, the conductive fill material 270comprises one or more of copper (Cu), cobalt (Co), ruthenium (Ru),tungsten (W), and molybdenum (Mo).

In some embodiments, the feature 240 comprises a bottom portion and atop portion. In some embodiments, the bottom portion comprises a via. Insome embodiments, the top portion comprises a trench. In someembodiments, a first conductive fill material is grown in a bottom-upmanner to fill the via portion that makes up the lower portion of thefeature 240. In some embodiments, a second conductive material isdeposited in the upper portion. In some embodiments, the firstconductive material and the second conductive material are same. In someembodiments, the first conductive material and the second conductivematerial are different. In some embodiments, the entire feature 240 isfilled with a single conductive material at one time to fill the lowerportion and upper portion of the feature 240 in one process.

The conductive material 270 can be deposited by any suitable techniqueknown to the skilled artisan. In some embodiments, the conductivematerial 270 is deposited by one or more of a chemical vapor deposition(CVD) process, an atomic layer deposition (ALD) process, or a physicalvapor deposition (PVD) process. In some embodiments, the conductivematerial 270 is deposited to overfill the feature 240 and form anoverburden on the surface of the substrate 210. The overburden is thenremoved by any suitable technique (e.g., etching, chemical-mechanicalplanarization (CMP)).

Without intending to be bound by theory, it is believed that theself-assembled monolayer (SAM) 255 increases the resistance of theconductive fill material 270 only marginally when compared to theincrease in resistance typically seen with most barrier layers (e.g.,film 260). Accordingly, the removal of the self-assembled monolayer(SAM) 255 is an optional process which may further decrease theresistance of the conductive fill material 270. In some embodiments, theremoval of the self-assembled monolayer (SAM) 255 decreases a resistanceof the metal interconnect 270 by 30%, 20%, 10% or 5%.

Additional embodiments of the disclosure are directed to processingtools 900 for the formation of the devices and methods described, asshown in FIG. 3 . A variety of multi-processing platforms, including theCentura®, Dual ACP, Producer® GT, and Endura® platform, available fromApplied Materials® as well as other processing systems may be utilized.In one or more embodiments, the cluster tool 900 includes at least onecentral transfer station 921, 931 with a plurality of sides. A robot925, 935 is positioned within the central transfer station 921, 931 andis configured to move a robot blade and a wafer to each of the pluralityof sides.

The cluster tool 900 comprises a plurality of processing chambers 902,904, 906, 908, 910, 912, 914, 916, and 918, also referred to as processstations, connected to the central transfer station. The variousprocessing chambers provide separate processing regions isolated fromadjacent process stations. The processing chamber can be any suitablechamber including, but not limited to, a selective metal depositionchamber; a barrier metal deposition chamber; a metal deposition chamber;a PVD metal deposition chamber; a CVD metal deposition chamber; aself-assembled monolayer (SAM) deposition chamber; a liner metaldeposition chamber; a plasma chamber; a pre-clean chamber; an etchingchamber; transfer space(s), a wafer orienter/degas chamber, a cryocooling chamber, and the like. The particular arrangement of processchambers and components can be varied depending on the cluster tool andshould not be taken as limiting the scope of the disclosure.

In one or more embodiments, the cluster tool 900 includes aself-assembled monolayer (SAM) deposition chamber to expose thesubstrate to a planar hydrocarbon and form a self-assembled monolayer(SAM). In one or more embodiments, the cluster tool 900 includes apre-cleaning chamber connected to the central transfer station.

In the embodiment shown in FIG. 3 , a factory interface 950 is connectedto a front of the cluster tool 900. The factory interface 950 includes aloading chamber 954 and an unloading chamber 956 on a front 951 of thefactory interface 950. While the loading chamber 954 is shown on theleft and the unloading chamber 956 is shown on the right, those skilledin the art will understand that this is merely representative of onepossible configuration.

The size and shape of the loading chamber 954 and unloading chamber 956can vary depending on, for example, the substrates being processed inthe cluster tool 900. In the embodiment shown, the loading chamber 954and unloading chamber 956 are sized to hold a wafer cassette with aplurality of wafers positioned within the cassette.

A robot 952 is within the factory interface 950 and can move between theloading chamber 954 and the unloading chamber 956. The robot 952 iscapable of transferring a wafer from a cassette in the loading chamber954 through the factory interface 950 to load lock chamber 960. Therobot 952 is also capable of transferring a wafer from the load lockchamber 962 through the factory interface 950 to a cassette in theunloading chamber 956. As will be understood by those skilled in theart, the factory interface 950 can have more than one robot 952. Forexample, the factory interface 950 may have a first robot that transferswafers between the loading chamber 954 and load lock chamber 960, and asecond robot that transfers wafers between the load lock 962 and theunloading chamber 956.

The cluster tool 900 shown has a first section 920 and a second section930. The first section 920 is connected to the factory interface 950through load lock chambers 960, 962. The first section 920 includes afirst transfer chamber 921 with at least one robot 925 positionedtherein. The robot 925 is also referred to as a robotic wafer transportmechanism. The first transfer chamber 921 is centrally located withrespect to the load lock chambers 960, 962, process chambers 902, 904,916, 918, and buffer chambers 922, 924. The robot 925 of someembodiments is a multi-arm robot capable of independently moving morethan one wafer at a time. In one or more embodiments, the first transferchamber 921 comprises more than one robotic wafer transfer mechanism.The robot 925 in first transfer chamber 921 is configured to move wafersbetween the chambers around the first transfer chamber 921. Individualwafers are carried upon a wafer transport blade that is located at adistal end of the first robotic mechanism.

After processing a wafer in the first section 920, the wafer can bepassed to the second section 930 through a pass-through chamber. Forexample, chambers 922, 924 can be uni-directional or bi-directionalpass-through chambers. The pass-through chambers 922, 924 can be used,for example, to cryo cool the wafer before processing in the secondsection 930 or allow wafer cooling or post-processing before moving backto the first section 920.

A system controller 990 is in communication with the first robot 925,second robot 935, first plurality of processing chambers 902, 904, 916,918 and second plurality of processing chambers 906, 908, 910, 912, 914.The system controller 990 can be any suitable component that can controlthe processing chambers and robots. For example, the system controller990 can be a computer including a central processing unit, memory,suitable circuits, and storage.

Processes may generally be stored in the memory of the system controller990 as a software routine that, when executed by the processor, causesthe process chamber to perform processes of the present disclosure. Thesoftware routine may also be stored and/or executed by a secondprocessor (not shown) that is remotely located from the hardware beingcontrolled by the processor. Some or all of the method of the presentdisclosure may also be performed in hardware. As such, the process maybe implemented in software and executed using a computer system, inhardware as, e.g., an application specific integrated circuit or othertype of hardware implementation, or as a combination of software andhardware. The software routine, when executed by the processor,transforms the general-purpose computer into a specific purpose computer(controller) that controls the chamber operation such that the processesare performed.

In one or more embodiments, the processing tool 900 comprises a centraltransfer station 921, 931 comprising at least one robot 925, 935configured to move a wafer; one or more of a selective via fill station,a reversely selective deposition station, a self-assembled monolayer(SAM) formation station, a CVD station, a PVD station connected to thecentral transfer station; an optional pre-clean station connected to thecentral transfer station; and at least one controller connected to theone or more of the central transfer station, selective via fill station,a reversely selective deposition station, a self-assembled monolayer(SAM) formation station, a CVD station, a PVD station or the optionalpre-clean station. In one or more embodiments, the at least onecontroller has at least one configuration selected from: a configurationto move the wafer between stations using the robot; a configuration toselectively fill a via; a configuration to expose a substrate to aplanar hydrocarbon and form a self-assembled monolayer (SAM); aconfiguration for reversely selective deposition of a barrier layer; aconfiguration to deposit a metal; and a configuration to pre-clean thewafer.

In one or more embodiments, a processing tool comprises: a pre-cleanchamber having a substrate support therein; a selective metal depositionchamber; a barrier metal deposition chamber; a metal deposition chamber;a PVD metal deposition chamber; a CVD metal deposition chamber;optionally, a self-assembled monolayer (SAM) deposition chamber with anoptional pre-clean; optionally, a liner metal deposition chamber;optionally, a plasma chamber; optionally, an etching chamber; a robotconfigured to access the pre-clean chamber, the selective depositionchamber, the optional self-assembled monolayer (SAM) deposition chamber,the barrier metal deposition chamber, the PVD metal deposition chamber,the optional plasma chamber; and the optional etching chamber, theoptional liner metal deposition chamber, the CVD metal depositionchamber and the PVD metal deposition chamber; and a controller connectedto the pre-clean chamber, the selective deposition chamber, the optionalself-assembled monolayer (SAM) deposition chamber, the barrier metaldeposition chamber, the PVD metal deposition chamber, the optionalplasma chamber; and the optional etching chamber, the optional linermetal deposition chamber, the CVD metal deposition chamber and the PVDmetal deposition chamber, and the robot, the controller having one ormore configurations selected from: cleaning a substrate, selectivelyforming a self-assembled monolayer (SAM), selectively depositing aliner, optionally forming a metal liner, forming a metallization layer,optional etching the substrate, and, optionally removing theself-assembled monolayer (SAM).

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe disclosure. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the disclosure.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the disclosure herein has been described with reference toparticular embodiments, those skilled in the art will understand thatthe embodiments described are merely illustrative of the principles andapplications of the present disclosure. It will be apparent to thoseskilled in the art that various modifications and variations can be madeto the method and apparatus of the present disclosure without departingfrom the spirit and scope of the disclosure. Thus, the presentdisclosure can include modifications and variations that are within thescope of the appended claims and their equivalents.

What is claimed is:
 1. A method of forming a semiconductor structure, the method comprising: selectively depositing a self-assembled monolayer (SAM) on a first surface of a substrate by exposing the substrate to a first precursor, wherein the substrate has at least one feature comprising the first surface and a second surface and wherein the first precursor has a structure of any of Formula (xiv), Formula (xvi), or Formula (xix) through Formula (xxvii)

wherein each n is independently 1-20 and each R is independently selected from H, C1-C10 alkyl or aryl groups; selectively depositing a liner on the second surface by exposing the substrate to a second precursor; and removing the self-assembled monolayer (SAM), wherein the first surface comprises a metal, and the second surface comprises a dielectric material.
 2. The method of claim 1, wherein selectively depositing the self-assembled monolayer (SAM) comprises forming the SAM on the first surface and not on the second surface.
 3. The method of claim 1, wherein selectively depositing the liner comprises forming the liner on the second surface and not on the first surface.
 4. The method of claim 1, further comprising cleaning the substrate before depositing the self-assembled monolayer (SAM) to form a substrate surface substantially free of oxide.
 5. The method of claim 1, wherein the first surface comprises one or more of copper (Cu), cobalt (Co), ruthenium (Ru), tungsten (W), and molybdenum (Mo).
 6. The method of claim 1, further comprising depositing an adhesion layer on the first surface and on the liner after removing the self-assembled monolayer (SAM).
 7. The method of claim 1, wherein the at least one feature comprises one or more of a trench and a via.
 8. The method of claim 1, further comprising depositing a conductive material in the at least one feature by exposing the substrate to a third precursor, the third precursor comprising a metal.
 9. The method of claim 8, wherein depositing the conductive material comprises one or more of a bottom-up gap fill and a conformal gap fill.
 10. The method of claim 1, wherein the first precursor is substantially free from one or more of metal, halogen or nitrogen, the substantially free refers to a less than 5% weight on atomic basis.
 11. The method of claim 1, wherein the first precursor comprises at least one unsaturated group.
 12. The method of claim 1, wherein the first precursor comprises at least one hydroxyl group.
 13. The method of claim 1, wherein the first precursor comprises at least one ether group.
 14. The method of claim 1, wherein the first precursor comprises at least one amine group.
 15. The method of claim 1, wherein a first precursor has a molecular weight in a range of from 50 Daltons to 500 Daltons.
 16. The method of claim 1, wherein the first precursor has a vapor pressure in a range of from 100 mTorr to 100 Torr at 120° C.
 17. A method of forming a semiconductor structure, the method comprising: exposing a substrate to at least one first precursor to selectively deposit a self-assembled monolayer (SAM) on a first surface of the substrate, the substrate having at least one feature comprising the first surface and a second surface; exposing the substrate to a second precursor to selectively deposit a liner on the second surface; and removing the self-assembled monolayer (SAM), wherein the first surface comprises a metal selected from one or more of copper (Cu), cobalt (Co), ruthenium (Ru), tungsten (W) and molybdenum (Mo), wherein the second surface comprises a dielectric material, wherein the first precursor has a molecular weight in a range of from 50 Daltons to 500 Daltons, and wherein the first precursor is selected from the group consisting of structures of Formula (xiv) or Formula (xvi)

wherein each n is independently 1-20 and each R is independently selected from H, C1-C10 alkyl or aryl groups.
 18. A method of forming a semiconductor structure, the method comprising: exposing a substrate to at least one first precursor to selectively deposit a self-assembled monolayer (SAM) on a first surface of the substrate, the substrate having at least one feature comprising the first surface and a second surface; exposing the substrate to a second precursor to selectively deposit a liner on the second surface; and removing the self-assembled monolayer (SAM), wherein the first surface comprises a metal selected from one or more of tungsten (W) and molybdenum (Mo), wherein the second surface comprises a dielectric material, wherein the first precursor has a vapor pressure in a range of from 100 mTorr to 100 Torr at 120° C., and wherein the first precursor is selected from the group consisting of structures of Formula (xix) through Formula (xxvii)

wherein each R is independently selected from H, C1-C10 alkyl or aryl groups. 